Modified linseed oil wrinkle finish



Patented Sept. 10, 1946 UNITED STATES PATENT OFFICE qtion'of Delaware ,No; Drawing. Original application ant-W31,

1942, SerialNo 42.9;116. Ilivideda id'tliis a'p-g: plication November 6, 1942; semi-1x1 464593:

6 Claims.

This application is a division of copending application Serial No. 429,116, filed January. 31, 1942, as a1continuation-in-part of copending application Serial No. 424,010 filed December 22, 1941;

This invention relates to wrinkle varnishbase and the primary purpose-thereof is'tl'ie preparation of a Wrinkle varnish base comprising the heat-reaction product of modified drying oil, oil soluble resin and air atelevated temperature.

Hitherto the preparation of wrinkle varnish base has been considered to requireth'e use of China-wood oil, oiticica oiland other similar drying oilscontaining conjugated double bonds, or mixtures of them. These-oils, or mixtures, were generally used either in their raw or natural state, or subsequent-to preliminary treatmentas by blowing, depending on the particular characteristics required in the finished wrinklevvarnish base and the nature of the individual oil or mi-x ture of oils being used.-

My copending application Serial No. 424,010 to which reference'has been made'hereinb'eioresets forth a method whereby wrinkle varnish base can be produced by chemically combining unblown drying-type oil with oil soluble resin and air at elevated temperature; the resulting product exhibiting excellent wrinkling tendency with theaddition of a small-amount of drier in'the usual manner. My present applicationdeals with an improved method in which chemically modified drying type oil is substituted for the unblown'drying type oil-(r theoil is modified in situl and a substantial-reduction is madein the cooking time for the varnish.

As typical examples of formulations and-procedures according to my present invention, but without thereby limiting myself. to the specific details. of procedure and proportions indicated, the. following illustrative examples :are: given:

Example'l' Wrinkling, resin 1bsl 100-125 Vegetable dryingoil gallonsls -35- Polyglycerol do 0.5-2- Hydrocarbon' solvent dollar 5-40 In preparing the'varnish base-from: the aiore mentioned; components approximately one-half of the oil and all of the resin are placed in a-kettle and heated rapidlyto400 F-. to obtain-atherough dispersion of the resin in the oil; Of course, if it is so desired, it is possible'to' disperse the resin in the entire quantity ofoil by following the same procedure; The polyglycerol "is then added to the batch and-the temperature inn 2 r creased to 540 where it-is held until a uni'-" form mixture has been obtainedas evidenced by the formation'oi a clear spot whenai drQp of-the mixture is dropped On' glassaiidallow'edtti cool.- Thereupon the batchis cooled to approximately 400 to 420 F. and bIOWl'i 'With air until'thedsired or required viscosity has been obtained. A satisfactory viscosity or end-point may be considered to have been reached-when a drop falls from a stirring rodwith a slight thread-jlike fil ament while hot. When this condition has been reached the mixture is -withdrawn from thefire andthe hydrocarbon solvent added ther" "of A suitable liquid drier shb'uld be added at"the'-'sa me time. In the case of Nuodex cobalt 6% liquid drier three fourths to one gallon would be re quired' for a batch such as that of ExampleI;

I Example 11 Ambero1801 -lbs' 10'0 Varnish grade linseed oil gal1ons 12 Polyglycerol d0 /1 Mineral spirits" do 5 Solvess'o' #2 ;-l do i6- Nuodex coba1t-6% do Example IV Amberol F7 1bs; '100 Varnish grade linseed oil; gallons; 15 Polyglycercl do' Mineral spirits do 5 Solvessd #2 l do' 16 0 Nuodex cobalt 6%; do

xample VI Amberol 801 lbs 100 Soya bean oil "gallons; 12" Polyglyc'erol do l Y5 Mineral spirits do 5 Solve'ss0# 2 do 16 Nuodexcobalt 6%"; "an--- The procedure followed in preparing the? wrinkle varnish base of my invention from the components given in Examples II to is sub stantially the same as that followedin Example I, although minor changes-in temperature and time of cooking are at times advantageous depending on the nature of the oil, being used.

It will be noted that in Exam t polyglycerol was incorporated in the mixture ";b mp1 d .jl

of oil and resin and cooked therein; This procedure is entirely satisfactory and economical l and represents one wherein the oil is modified in, situ; however, ingthe practice of my invention I ;,have obtained, equally satisfactory results by separately heating a mixture of drying oil and polyglycerol and using the mixture in the varnish formulation; The'procedure followed was substantially as given below: I

Ezrmnple-VI II I Gallons Vegetable drying oil Polyglycerol 1 Theabove mixture was heated to a temperature of approximately 500 to 520 F and held at substantially that temperature until a sample withdrawn from the batch. did not show any substantialseparation of polyg lycerol 1 and oil on cooling fanduntil a drop deposited on glass showed complete homogeneity. 'The resulting product was then used in-formulations such as the following; H

Example IX I Amberol 8'01 lbs 100 Productof Example VIII "gallons; 12 Mineral spirits do 5 Solvesso #2 r 1., do w 16 Nuodex cobalt 6% r 1 r do In preparing the wrinkle varnish base of my inventionfrom the components of Example IX the resin and modified drying oil were heated together at a temperature of approximately 400 C. until the resin became thoroughly dispersed-inthe oil. The temperature .was then increased to approximately 540 F. and held at that temperature until a clear spot formed when a drop was deposited on glass. The batch was then allowed to cool to approximately 400'F.-

h 7 Example}! 4 v I Glycerinv gallons 4 Sodium acetate lbs I The above mixture was heated slowly to 500 F. in minutes) and then allowed tocool.

I acterize the use of such oils.

As will be noted from the examples, maleic acid resin, as well as phenol-aldehyde resin, may be used satisfactorily in the practice of my invention. Maleic acid resin of the type commercially available and sold under trade names such as 'Amberol 801, Beckacite 1110,, B'eckacite 1111 and Beckacite 1114' may be employed, but, of course, other alkyd-resins made from combina- 'tions of rosin, polyhydric alcohols and polycar- 1o boxylic acids or anhydrides prove suitable. Like- 'wise,"oil solubleand non-reactive phenol-alde- .,hyde resins may ,be ,used in the practice of my "invention; :These-include resins known by trade names -such' as'Beckacite, Durez, Para-dura, Durite, Locto, Paranol, Varcum, etc. In every {case anoil'soluble' and non-reactive quality must It willbe understood by those skilled in the art that by mineral spirits is meant that grade of petroleum product of .either a paraffinic or naphthenic origin whichis commonly known'jin the trade as turpentine substitute; while Solvesso #Zlis av hydrogenated naphtha having a volatility similar to that .of xylol and manufactured by Standard Oil Company. Nuodex cobalt '6% is a cobaltnaphthenate drier solution, in which the metallic cobalt amounts to about 6%. H

The end-point of the blowing step employed in the practice of my invention may be deter; mined as previously mentioned herein; however,it may also be determined by other means, as, for instance, by withdrawing test samples from time to time during the blowing operation,"

adding a predetermined amount of thinner to a definite weight of sample, and comparing the viscosity I of the resulting solution with the Gardner-Holdt viscosity standards. V

The fundamental difierence between the meth-' od'of my ,invention, as disclosed; herein, andthe method disclosed and claimed in mycopending application Serial No. 424,010,; filed December 22, 1941, is that according to my present improved procedure, I am able toreduce the blowing time required to produce any predetermined bodyby, approximately one-half; therefore, ,the improved procedure which isthe subject matter .of. the present invention makes it possible to effect economies; in manufacture and substantially. increase the'output of the varnish kettles in any given plant. i v

The coatings produced with; the wrinkle varnish'base of the present invention yield hard, tough films, and since I employ unblown oils in the practice of my invention, I do notencounter the difiiculties and inconveniences which chars It. is well known that blown oils commonly used in the prior art exhibit auto-oxidizing tendencies due to the fact that they contain intermolecularly dispersed air which results in gradual andcontinuous oxida-- tion and also leads to separation of part of the oil as an insoluble gel, thus rendering the product-valuelessforuse in a varnish, and particularly so when the varnish is 'part of a sprayable composition. a r

In 'con-tradistinction, the product of my invention will preserve its homogeneous nature and will show no separation for an indefinite period of time. It will be noted that according to-my inventionv the oil, as such, is not submitted to aeration and that it is the cooked varnish that is blownwith air. I am unable to ofieriproof as to, the mechanism of the reaction which the oil undergoes when treated with ipolyglycerol. Likewise, Iam'unable to ofier proof as to the mechanism of. the reaction which the modified oil undergoes when-treated with air at elevated temperature in the presence of the synthetic resin as hereinbefore set forth. However, with'resp'ect to the latter, it is my opinion that due to the comparatively high temperature used in the blowing operation only that air which is chemically taken up by the mixture of modified oil and resin remains therein, since the temperature of treatment is sufficiently high to expel any uncombined air. This prevents the intermolecular dispersion of air which appears to be present in blown oils and leads to their continuous oxidation during storage.

It is well to reiterate that in the practice of my invention the oil, as such, is not aerated for it will be remembered that the modified oil and resin are conjointly aerated.

The selection of thinners to be used in the practice of my invention is not critical although preference should be given to those products of high volatility such as toluol, xylol, light naphtha, etc. Of course, a small quantity of low volatility solvent may prove of value to bring about a sudden chilling of a batch in order to check the bodying thereof in the event it should have been blown a trifle too long.

Many different driers may be used but preference should be given to those commonly known as top driers and which are characterized by a tendency to form the surface skin which is so desirable in wrinkle compositions. The resinate, linoleate and naphthenate type of drier, characterized by ready solubility, proves very suitable for this purpose.

It will be understood that while I have given typical examples using certain oils, it is not my intention to limit myself to the use of such oils in view of the fact that other drying oils are susceptible to the same treatment and may be used in the practice of my invention. The choice of oil will depend primarily on availability and cost. Those skilled in the art will understand that the Castung Z-3 used in Example III is a commercial grade of dehydrated castor oil.

The choice of resin will depend on the desired characteristics of the wrinkle varnish base. As has been noted hereinbefore, rosin modified alkyd resin such as maleic acid resin may be used satisfactorily and it will be understood that other polycarboxylic acids or their anhydrides including phthalic, tartaric, citric and malic may be substituted for the maleic acid or anhydride, although the rosin modified maleic acid resin is preferred from among the alkyd resins. Likewise, other phenol-aldehyde resins may be used in place of that mentioned in the examples.

Furthermore, natural resins such as Congo, Kauri, Batu, Zanzibar, oil soluble Manila, Pontianak, etc. may be employed, but where such resins are used they should first be run to make them oil soluble and the first step of the process hereinbefore described would have to be altered accordingly. In such case, for example, the resin would first be fused and then added to the heated oil and the temperature raised to a point sufiicient to dissolve the resin in the oil. The necessity for pretreating the natural resin will be fully appreciated by those skilled in the art.

The products resulting from the practice of my invention are adapted for use as clear wrinkle finishes without further treatment. They may be further compounded with pigment ground in oil vehicle for the purpose of producing wrinkling enamels, and-texture modifying ingredients of various sorts maybe incorporated; therein.

1 As has been mentioned hereinbefore, I am un able to giveany explanation or set forth the mechanics of the reactions which take place when dehydrated 'gly'cerol or polyglycerol is reacted with the drying oil, but it is reasonable to assume that there is esterification of the oil with the formation of di-glycerides and perhaps of monoglycerides.

The most significant thing about the present invention is that I make use of oils which are plentifully available from domestic sources and which are characterized by substantial stability of quality and cost. In addition, these oils have never been considered suitable for use in the production of wrinkling varnishes without first blowing them in view of the fact that the unblown oils have always produced smooth, glossy films such as those which characterize linseed oil. It may be said, therefore, that according to my invention it is possible to produce wrinkling varnishes from unblown drying oils which hitherto have been considered unsuitable for the purpose without prior blowing thereof and which have been hitherto considered inhibitors of wrinkle formation. Therefore, the substance of my invention is that I have obtained an unexpected result contrary to the teachings and skill of the art.

Wrinkle coating compositions produced using the Wrinkle varnish base of my invention are adapted to be sprayed and then baked at temperatures of from 200 to 250 F. for approximately one hour to produce a wrinkle finish characterized by its toughness and hardness.

It will be understood that while I have set forth certain specific embodiments of my invention, it is not my intention to have it limited to or circumscribed by the specific details of procedure and proportions indicated in view of the fact that my invention is adapted to changes according to individual preference and conditions without departing from the scope thereof as defined in the appended claims.

I claim:

1. The method of making wrinkle varnish base consisting in heating glycerine with a dehydrating agent from the group consisting of sodium acetate and sodium hydroxide to approximately 500 F. for about 30 minutes, adding non-conjugated double-bonded drying oil and heating to approximately 500 to 520 F.; adding natural resin and heating to approximately 540 F., and blowing the reaction mixture with air at about 400 to 420 F.

2. The method of making wrinkle varnish base consisting in heating approximately 4 gallons of glycerine with lb. of a dehydrating agent from the group consisting of sodium acetate and sodium hydroxide to approximately 500 F. for about 30 minutes; adding per one part by volume of the mixture thus obtained 20 parts by volume of non-conjugated double-bonded drying oil and heating the mixture to approximately 500 to 520 F.; thereafter adding oil soluble natural resin and heating to approximately 540 F.; and then blowing the reaction mixture with air at about 400 to 420 F.

3. A pro-duct obtained by the process of claim 1.

4. A product obtained by the process of claim 2.

5. The method of making wrinkle varnish base consisting in heating approximately 4 gallons of glycerine with pound of dehydrating agent from the group consisting of sodium acetate and sodium hydroxide to approximately 500 F. for about; 30 minutes; adding to 0.5 to 2 gallons of the mixture thus obtained 10 to 35 gallons of non-conjugated double-bonded drying oil and heating the mixture to approximately 500 to 520 F.; thereafter adding 100 to 125 pounds of oil soluble natural resin and heating to approxi-: mately 540 F.; and then blowing the'reaction .WILLIAM A. WALDIVEL 

